243 research outputs found

    A Tribute to Sibby Whitten

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    Safe labs for science: An interactive approach to safety training

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    Safe working in Chemistry involves critical analysis, interactive thinking and the evolving application of risk assessment to procedure, reagent and environment. It also requires cooperation and teamwork. These are transferable skills that all scientists should possess, but safety training is too often presented to undergraduate students as a set of rules with little rationale offered to justify them. Attempts to go beyond a set of rules are frequently perceived by students and academics as tedious if not outright boring – however necessary they may be. We describe the first stages of development of a safety training component for mainstream Chemistry courses that will allow students to identify safe and unsafe practices, undertake formal risk assessment, and enable them to improve the safety of their own environment. Our starting point is a Safety Training Workshop for our own 3rd year undergraduates, including case studies, a (competitive) team exercise (a lab ‘scavenger hunt’) and electronic self-testing, designed to alleviate the tedium. They also emphasise the cooperative nature of safe working and encourage teamwork – aspects which are normally neglected in degree programmes in Science. We also report on the positive student response

    One-pot access to L-5,6-dihalotryptophans and L-alknyltryptophans using tryptophan synthase

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    The authors thank the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013/ERC grant agreement no 614779, and the University of St Andrews for a studentship (to D. R. M. Smith).We report, for the first time, the use of tryptophan synthase in the generation of L- dihalotryptophans and L-alkynyltryptophans. These previously unpublished compounds will be useful tools in the generation of probes for chemical biology, in biosynthetic diversification and as convenient building blocks for synthesis.PostprintPeer reviewe

    Alcohol advertising during televised Australian Football finals

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    Alcohol marketing during sport, and alcohol industry sponsorship of sporting events, is highly lucrative; however, concerns have been raised over the impact on child and adolescent viewers of repeated exposure to alcohol marketing messages. The aim of this research project was to investigate the amount and type of alcohol marketing during two major sporting events in 2012 - the semi-finals and grand final of the AFL and NRL. The broadcasts of these six games were audited for alcohol advertisements and other advertising communications. Almost one-fifth of the screen time included alcohol marketing. Policy and practice implications of these findings are discussed

    Spectral absorption of biomass burning aerosol determined from retrieved single scattering albedo during ARCTAS

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    Actinic flux, as well as aerosol chemical and optical properties, were measured aboard the NASA DC-8 aircraft during the ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) mission in Spring and Summer 2008. These measurements were used in a radiative transfer code to retrieve spectral (350-550 nm) aerosol single scattering albedo (SSA) for biomass burning plumes encountered on 17 April and 29 June. Retrieved SSA values were subsequently used to calculate the absorption Angstrom exponent (AAE) over the 350-500 nm range. Both plumes exhibited enhanced spectral absorption with AAE values that exceeded 1 (6.78 ± 0.38 for 17 April and 3.34 ± 0.11 for 29 June). This enhanced absorption was primarily due to organic aerosol (OA) which contributed significantly to total absorption at all wavelengths for both 17 April (57.7%) and 29 June (56.2%). OA contributions to absorption were greater at UV wavelengths than at visible wavelengths for both cases. Differences in AAE values between the two cases were attributed to differences in plume age and thus to differences in the ratio of OA and black carbon (BC) concentrations. However, notable differences between AAE values calculated for the OA (AAEOA) for 17 April (11.15 ± 0.59) and 29 June (4.94 ± 0.19) suggested differences in the plume AAE values might also be due to differences in organic aerosol composition. The 17 April OA was much more oxidized than the 29 June OA as denoted by a higher oxidation state value for 17 April (+0.16 vs. -0.32). Differences in the AAEOA, as well as the overall AAE, were thus also possibly due to oxidation of biomass burning primary organic aerosol in the 17 April plume that resulted in the formation of OA with a greater spectral-dependence of absorption. © Author(s) 2012. CC Attribution 3.0 License

    Fluorine in fragrances : exploring the difluoromethylene (CF2) group as a conformational constraint in macrocyclic musk lactones

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    The authors thank EPSRC for a grant. CNvH also thanks the Fluorine Division of the American Chemical Society for a Moissan Summer Undergraduate Fellowship. RAC thank FAPESP for a fellowship (#2015/00975-7).The CF2 group is incorporated into specific positions within the lactone ring of the natural musk lactone, (12R)-(+)-12-methyl-13-tridecanolide, a constituent of Angelica root oil, Angelica archangelica L. The approach is taken as it was anticipated that CF2 groups would dictate corner locations in the macrocycle and limit the conformational space available to the lactone. Three fluorine containing lactones are prepared by organic synthesis. One (8) has CF2 groups located at the C-6 and C-9 positions, another (9) with CF2 groups at the C-5 and C-9 positions, and a third (10) with a CF2 group at C-8. Two of the fluorine containing lactones (8 and 10) were sufficiently crystalline to obtain X-ray crystal structures which revealed that the CF2 groups do adopt corner locations. All three lactones were subject to computational analysis at the B3LYP-D3/6-311+G** level to assess the relative energies of different conformers. In all cases, the global minima and most of the lowest energy minima have squared /rectangular geometries and located the CF2 groups at the corners. The lowest energy structures for 8 and 10 closely approximated the observed X-ray structures, suggesting good convergence of theory and experiment in determining relevant low energy conformations. All three compounds retained a pleasant odour suggesting the rings retained sufficient conformational flexibility to access relevant olfactory conformations.Publisher PDFPeer reviewe

    Mast Cell-Mediated Inhibition of Abdominal Neutrophil Inflammation by a PEGylated TLR7 Ligand

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    Although the mechanisms for sustained chemokine gradients and recurring cell infiltration in sterile peritonitis have not been elucidated, toll-like receptors (TLRs) have been implicated. To abate the deleterious recruitment of neutrophils in sterile inflammation, we repeatedly administered a TLR7 ligand that hyposensitized to TLR7 and receptors that converged on the MyD88-signaling intermediary and reduced cellular infiltration in murine autoimmune models of multiple sclerosis and arthritis. To reduce potential adverse effects, a polyethylene glycol polymer was covalently attached to the parent compound (Tolerimod1). The proinflammatory potency of Tolerimod1 was 10-fold less than the unconjugated TLR7 ligand, and Tolerimod1 reduced neutrophil recruitment in chemically induced peritonitis and colitis. The effects of Tolerimod1 were mediated by the radioresistant cells in radiation chimeric mice and by mast cells in reconstituted mast cell-deficient mice (KitW-sh). Although the Tolerimod1 had weak proinflammatory agonist activity, it effectively reduced neutrophil recruitment in sterile peritoneal inflammation

    Small conductance calcium-activated potassium current is important in transmural repolarization of failing human ventricles

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    BACKGROUND: The transmural distribution of apamin-sensitive small conductance Ca(2+)-activated K(+) (SK) current (IKAS) in failing human ventricles remains unclear. METHODS AND RESULTS: We optically mapped left ventricular wedge preparations from 12 failing native hearts and 2 rejected cardiac allografts explanted during transplant surgery. We determined transmural action potential duration (APD) before and after 100 nmol/L apamin administration in all wedges and after sequential administration of apamin, chromanol, and E4031 in 4 wedges. Apamin prolonged APD from 363 ms (95% confidence interval [CI], 341-385) to 409 (95% CI, 385-434; P<0.001) in all hearts, and reduced the transmural conduction velocity from 36 cm/s (95% CI, 30-42) to 32 cm/s (95% CI, 27-37; P=0.001) in 12 native failing hearts at 1000 ms pacing cycle length (PCL). The percent APD prolongation is negatively correlated with baseline APD and positively correlated with PCL. Only 1 wedge had M-cell islands. The percentages of APD prolongation in the last 4 hearts at 2000 ms PCL after apamin, chromanol, and E4031 were 9.1% (95% CI, 3.9-14.2), 17.3% (95% CI, 3.1-31.5), and 35.9% (95% CI, 15.7-56.1), respectively. Immunohistochemical staining of subtype 2 of SK protein showed increased expression in intercalated discs of myocytes. CONCLUSIONS: SK current is important in the transmural repolarization in failing human ventricles. The magnitude of IKAS is positively correlated with the PCL, but negatively correlated with APD when PCL is fixed. There is abundant subtype 2 of SK protein in the intercalated discs of myocytes
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